Oxidation dyeing process implementing a pretreatment based on a composition rich in fatty substances and on metal catalysts

ABSTRACT

The present invention relates to a process for the oxidation dyeing of keratin fibres implementing: a) a step of pretreating said fibres by application to said fibres of a cosmetic composition (B) comprising: i) at least one fatty substance in an amount of greater than or equal to 10% by weight relative to the total weight of the composition (B); and ii) at least one metal catalyst; b) optionally a washing, rinsing, drying and/or rubbing-dry step; c) followed by a step of dyeing by application to said fibres of a cosmetic composition (A) comprising: i) at least one oxidation base, preferably chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases preferably comprising at least two nitrogen atoms, and addition salts thereof; ii) optionally at least one coupler; and iii) at least one chemical oxidizing agent. The dyeing process makes it possible to significantly improve the dyeing properties of the colouration, in particular in terms of selectivity, of chromaticity, and of colour intensity and uptake. The use of a composition which is rich in fatty substances, i.e. greater than 10%, and contains at least one catalyst pretreatment, before oxidation dyeing, allows a clear improvement in the dyeing properties, in particular in terms of dye uptake onto keratin fibres, of strength and of chromaticity and of selectivity of the colour.

The present invention relates to a process for the oxidation dyeing ofkeratin fibres implementing a pretreatment step based on a compositionrich in fatty substances and comprising one or more metal catalyst(s).

Many people have sought for a long time to modify the colour of theirhair and in particular to mask their grey hair.

It is known practice to obtain “permanent” or oxidation colourationswith dyeing compositions containing oxidation dye precursors, which aregenerally known as oxidation bases, such as ortho- orpara-phenylenediamines, ortho- or para-aminophenols and heterocycliccompounds. These oxidation bases are initially colourless or weaklycoloured compounds, which, when combined with oxidizing products, maygive rise to coloured compounds via a process of oxidative condensation.

It is also known that the shades obtained with these oxidation bases canbe varied by combining them with couplers or colouration modifiers, thelatter being chosen in particular from aromatic meta-diamines,meta-aminophenols, meta-diphenols and certain heterocyclic compounds,such as indole compounds. The variety of molecules used as oxidationbases and couplers allows a wide range of colours to be obtained.

The permanent dyeing process thus consists in applying, to the keratinfibres, bases or a mixture of bases and couplers with hydrogen peroxide(H₂O₂ or aqueous hydrogen peroxide solution), as oxidizing agent, inleaving to diffuse, and in then rinsing the fibres. The colourationswhich result therefrom have the advantage of being permanent, strong andresistant to external agents, in particular to light, bad weather,washing operations, perspiration and rubbing actions.

However, it is still sought to increase the efficiency of the reactionof the oxidation dyes used during this process in order to improve theiruptake on keratin fibres. Indeed, such an improvement would make itpossible in particular to decrease the contents of the oxidation dyespresent in dyeing compositions, to reduce the leave-on time on keratinfibres and/or to use other dye families which have a weak dyeingcapacity but which are capable of exhibiting a good toxicologicalprofile, of providing new shades or of producing colourations which areresistant with respect to external agents such as light or shampoos.

In this regard, it has already been proposed to use cosmeticcompositions containing metal catalysts during a dyeing process in orderto accelerate the dye oxidation reaction and to improve the intensity ofthe colouration on the keratin fibres. However, the dyeing powerobtained is still not entirely satisfactory and the colourationsobtained are generally too selective, i.e. these colourations are notuniform along the keratin fibre.

There is therefore a real need to provide a process for dyeing keratinfibres which is carried out in the presence of an oxidizing agent andwhich does not have the drawbacks of the existing processes, i.e. whichis capable of resulting in a satisfactory intensity of the oxidationdyes on the keratin fibres while at the same time resulting inrelatively non-selective colourations.

Moreover, oxidation dyeing processes are known which implement apretreatment step using a composition containing metal derivatives ofmanganese/cerium type and oxidation colourations. The pretreatmentcompositions generally consist of mixtures of water with alcohols (see,for example, WO 2003/011237, WO 97/022008), or in the presence of oil(WO 93/18738). Nevertheless, the colours obtained are not alwayssatisfactory, in particular in terms of colour variety, coverage of greyhair, chromaticity, colouration intensity and/or selectivity.

This (these) aim(s) is (are) achieved by the present invention, onesubject of which is a process for the oxidation dyeing of keratinfibres, in particular human keratin fibres such as the hair,implementing:

-   -   a) a step of pretreating said fibres by application to said        fibres of a cosmetic composition (B) comprising:        -   i) at least one fatty substance preferably in an amount of            greater than or equal to 10%, preferably greater than or            equal to 25%, more preferentially in an amount of greater            than or equal to 35% by weight relative to the total weight            of the composition (B); and        -   ii) at least one metal catalyst;    -   b) optionally a washing, rinsing, drying and/or rubbing-dry        step;    -   c) followed by a step of dyeing by application to said fibres of        a cosmetic composition        -   (A) comprising:        -   i) at least one oxidation base, preferably chosen from            para-phenylenediamines, bis(phenyl)alkylenediamines,            para-aminophenols, ortho-aminophenols, heterocyclic bases            preferably comprising at least two nitrogen atoms, and            addition salts thereof;        -   ii) optionally at least one coupler; and        -   iii) at least one chemical oxidizing agent.

The dyeing process makes it possible to significantly improve the dyeingproperties of the colouration, in particular in terms of selectivity,i.e. colourations which are uniform along the keratin fibre, ofchromaticity, and of colour intensity and uptake.

The use of a composition which is rich in fatty substances, i.e. greaterthan 10%, and contains at least one catalyst, as a pretreatment, beforeoxidation dyeing, allows a clear improvement in the dyeing properties,in particular in terms of dye uptake onto keratin fibres, of strengthand of chromaticity and of selectivity of the colour.

Moreover, the dyeing process according to the invention makes itpossible to improve the intensity of the colouration on the keratinfibres compared with a conventional dyeing process.

The present invention also relates to a multicompartment devicecomprising a first compartment containing a composition (B) aspreviously defined, a second compartment containing a composition (A′)comprising i) one or more oxidation bases, preferably chosen frompara-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols,ortho-aminophenols, heterocyclic bases preferably comprising at leasttwo nitrogen atoms, and addition salts thereof, ii) optionally one ormore couplers and iv) optionally one or more organic or inorganicalkaline agents; and a third compartment containing a composition (C)comprising one or more oxidizing agents.

According to one particular embodiment, the device comprises a fourthcompartment comprising a composition (D) comprising one or more fattysubstances, said composition (D) to be mixed with the compositions (A′)and (C), the fatty substance content being greater than or equal to 10%by weight relative to the total weight of the mixture of thecompositions (A′), (C) and (D), the composition (A′) or (C) possiblycontaining one or more fatty substances.

Other characteristics and advantages of the invention will emerge moreclearly on reading the description and the examples that follow.

In that which follows and unless otherwise indicated, the limits of arange of values are included in this range.

The expression “at least one” is equivalent to the expression “one ormore”.

The composition (B) used in the invention comprises i) at least 10% offatty substances and ii) at least one metal catalyst.

i) Fatty Substance(s):

The term “fatty substance” is intended to mean an organic compound thatis insoluble in water at ordinary ambient temperature (25° C.) and atatmospheric pressure (760 mmHg) (solubility of less than 5%, preferablyless than 1% and even more preferentially less than 0.1%). They have intheir structure at least one hydrocarbon-based chain comprising at least6 carbon atoms or a sequence of at least two siloxane groups. Inaddition, the fatty substances are generally soluble in organic solventsunder the same temperature and pressure conditions, for instancechloroform, ethanol, benzene, liquid petroleum jelly ordecamethylcyclopentasiloxane.

These fatty substances are neither polyoxyethylenated norpolyglycerolated. They are different from fatty acids since salifiedfatty acids constitute soaps which are generally soluble in aqueousmedia.

The fatty substances are in particular chosen from C₆-C₁₆ hydrocarbonsor hydrocarbons containing more than 16 carbon atoms and in particularalkanes, oils of animal origin, oils of plant origin, fluoro oils orglycerides of synthetic origin, fatty alcohols, fatty acid and/or fattyalcohol esters, non-silicone waxes, and silicones.

It is recalled that, for the purposes of the invention, the fattyalcohols, fatty esters and fatty acids more particularly contain one ormore linear or branched, saturated or unsaturated hydrocarbon-basedgroups containing 6 to 30 carbon atoms, which is (are) optionallysubstituted, in particular with one or more hydroxyl groups (inparticular 1 to 4). If they are unsaturated, these compounds maycomprise one to three conjugated or non-conjugated carbon-carbon doublebonds.

As regards the C₆-C₁₆ alkanes, they are linear or branched, and possiblycyclic. Examples that may be mentioned include hexane, dodecane,undecane, tridecane, and isoparaffins, for instance isohexadecane andisodecane. The linear or branched hydrocarbons containing more than 16carbon atoms may be chosen from liquid paraffins, petroleum jelly,liquid petroleum jelly, polydecenes, and hydrogenated polyisobutene suchas Parleam®.

According to one particular embodiment, the fatty substance(s) used inthe process of the invention is (are) chosen from volatile linearalkanes.

The term “one or more volatile linear alkane(s)” is intended to mean,without preference, “one or more volatile linear alkane oil(s)”.

A volatile linear alkane that is suitable for the invention is liquid atambient temperature (about 25° C.) and at atmospheric pressure (101 325Pa or 760 mmHg).

The term “volatile linear alkane that is suitable for the invention” isintended to mean a linear alkane that can evaporate on contact with theskin in less than one hour, at ambient temperature (25° C.) andatmospheric pressure (101 325 Pa), which is liquid at ambienttemperature, in particular having an evaporation rate ranging from 0.01to 15 mg/cm²/minute, at ambient temperature (25° C.) and atmosphericpressure (101 325 Pa).

Preferably, the volatile linear alkanes that are suitable for theinvention have an evaporation rate ranging from 0.01 to 3.5mg/cm²/minute and better still from 0.01 to 1.5 mg/cm²/minute, atambient temperature (25° C.) and atmospheric pressure (101 325 Pa).

More preferably, the volatile linear alkanes that are suitable for theinvention have an evaporation rate ranging from 0.01 to 0.8mg/cm²/minute, preferentially from 0.01 to 0.3 mg/cm²/minute and evenmore preferentially from 0.01 to 0.12 mg/cm²/minute, at ambienttemperature (25° C.) and atmospheric pressure (101 325 Pa).

The evaporation rate of a volatile alkane in accordance with theinvention (and more generally of a volatile solvent) may in particularbe evaluated by means of the protocol described in WO 06/013 413, andmore particularly by means of the protocol described below.

15 g of volatile hydrocarbon-based solvent are placed in a crystallizingdish (diameter: 7 cm) placed on a balance that is in a chamber of about0.3 m³ which is temperature-regulated (25° C.) and hygrometry-regulated(50% relative humidity).

The volatile hydrocarbon-based solvent is allowed to evaporate freely,without stirring it, while providing ventilation by means of a fan(Papst-Motoren, reference 8550 N, rotating at 2700 rpm) placed in avertical position above the crystallizing dish containing the volatilehydrocarbon-based solvent, the blades being directed towards thecrystallizing dish, 20 cm away from the bottom of the crystallizingdish.

The weight of volatile hydrocarbon-based solvent remaining in thecrystallizing dish is measured at regular time intervals.

The evaporation profile of the solvent is then obtained by plotting thecurve of the amount of product evaporated (in mg/cm²) as a function oftime (in minutes).

The evaporation rate is then calculated, which corresponds to thetangent to the origin of the curve obtained. The evaporation rates areexpressed in mg of volatile solvent evaporated per unit of area (cm²)and per unit of time (minutes).

According to one preferred embodiment, the volatile linear alkanes thatare suitable for the invention have a non-zero vapour pressure (alsoknown as saturation vapour pressure), at ambient temperature, inparticular a vapour pressure ranging from 0.3 Pa to 6000 Pa.

Preferably, the volatile linear alkanes that are suitable for theinvention have a vapour pressure ranging from 0.3 to 2000 Pa and betterstill from 0.3 to 1000 Pa, at ambient temperature (25° C.).

More preferably, the volatile linear alkanes that are suitable for theinvention have a vapour pressure ranging from 0.4 to 600 Pa,preferentially from 1 to 200 Pa and even more preferentially from 3 to60 Pa, at ambient temperature (25° C.).

According to one embodiment, a volatile linear alkane that is suitablefor the invention may have a flash point that is in the range of from 30to 120° C. and more particularly from 40 to 100° C. The flash point isin particular measured according to standard ISO 3679.

According to one embodiment, the volatile linear alkanes that aresuitable for the invention may be linear alkanes comprising from 7 to 15carbon atoms, preferably from 8 to 14 carbon atoms and better still from9 to 14 carbon atoms.

More preferably, the volatile linear alkanes that are suitable for theinvention may be linear alkanes comprising from 10 to 14 carbon atomsand even more preferentially from 11 to 14 carbon atoms.

A volatile linear alkane that is suitable for the invention mayadvantageously be of plant origin.

Preferably, the volatile linear alkane or the mixture of volatile linearalkanes present in the composition according to the invention comprisesat least one ¹⁴C (carbon-14) carbon isotope. In particular, the ¹⁴Cisotope may be present in a ¹⁴C/¹²C isotope ratio by number of greaterthan or equal to 1×10⁻¹⁶, preferably greater than or equal to 1×10⁻¹⁵,more preferably greater than or equal to 7.5×10⁻¹⁴ and better stillgreater than or equal to 1.5×10⁻¹³. Preferably, the ¹⁴C/¹²C ratio rangesfrom 6×10⁻¹³ to 1.2×10⁻¹².

The amount of ¹⁴C isotopes in the volatile linear alkane or the mixtureof volatile linear alkanes may be determined via methods known to thoseskilled in the art such as the Libby compacting method, liquidscintillation spectrometry or accelerator mass spectrometry.

Such an alkane may be obtained, directly or in several steps, from aplant raw material, such as an oil, a butter, a wax, etc.

As examples of alkanes that are suitable for the invention, mention maybe made of the alkanes described in patent applications WO 2007/068 371and WO 2008/155 059. These alkanes are obtained from fatty alcohols,which are themselves obtained from coconut oil or palm oil.

As examples of linear alkanes that are suitable for the invention,mention may be made of n-heptane (C7), n-octane (C8), n-nonane (C9),n-decane (C10), n-undecane (C11), n-dodecane (C12), n-tridecane (C13),n-tetradecane (C14), and n-pentadecane (C15) and mixtures thereof.According to one particular embodiment, the volatile linear alkane ischosen from n-nonane, n-undecane, n-dodecane, n-tridecane andn-tetradecane, and mixtures thereof.

According to one preferred embodiment, mention may be made of mixturesof n-undecane (C11) and of n-tridecane (C13) obtained in Examples 1 and2 of application WO 2008/155 059.

Mention may also be made of n-dodecane (C12) and n-tetradecane (C14)sold, respectively, under the references Parafol 12-97 and Parafol 14-97by the company Sasol, and also mixtures thereof.

One embodiment consists in using only one volatile linear alkane.

Alternatively, a mixture of at least two different volatile linearalkanes, differing from each other by a carbon number n of at least 1,in particular differing from each other by a carbon number of 1 or 2,may be used.

According to one embodiment, a mixture of at least two differentvolatile linear alkanes comprising from 10 to 14 carbon atoms anddiffering from each other by a carbon number of at least 1, is used.Examples that may in particular be mentioned include mixtures ofC10/C11, C11/C12 or C12/C13 volatile linear alkanes.

According to another embodiment, a mixture of at least two differentvolatile linear alkanes comprising from 10 to 14 carbon atoms anddiffering from each other by a carbon number of at least 2 is used.Examples that may in particular be mentioned include mixtures of C10/C12or C12/C14 volatile linear alkanes, for an even carbon number n and theC11/C13 mixture for an odd carbon number n.

According to one preferred embodiment, a mixture of at least twodifferent volatile linear alkanes comprising from 10 to 14 carbon atomsand differing from each other by a carbon number of at least 2, and inparticular a mixture of C11/C13 volatile linear alkanes or a mixture ofC12/C14 volatile linear alkanes, is used.

Other mixtures combining more than two volatile linear alkanes accordingto the invention, for instance a mixture of at least three differentvolatile linear alkanes comprising from 7 to 15 carbon atoms anddiffering from each other by a carbon number of at least 1, may be usedin the invention.

In the case of mixtures of two volatile linear alkanes, said twovolatile linear alkanes preferably represent more than 95% and betterstill more than 99% by weight of the mixture.

According to one particular embodiment of the invention, in a mixture ofvolatile linear alkanes, the volatile linear alkane having the smallestcarbon number is predominant in the mixture.

According to another embodiment of the invention, a mixture of volatilelinear alkanes in which the volatile linear alkane having the largestcarbon number is predominant in the mixture is used.

As examples of mixtures that are suitable for the invention, mention maybe made in particular of the following mixtures:

-   -   from 50% to 90% by weight, preferably from 55% to 80% by weight        and more preferentially from 60% to 75% by weight of Cn volatile        linear alkane with n ranging from 7 to 15,    -   from 10% to 50% by weight, preferably from 20% to 45% by weight        and preferably from 24% to 40% by weight of Cn+x volatile linear        alkane with x greater than or equal to 1, preferably x=1 or x=2,        with n+x between 8 and 14, relative to the total weight of the        alkanes in said mixture.

In particular, said mixture of volatile linear alkanes may also contain:

-   -   less than 2% by weight and preferably less than 1% by weight of        branched hydrocarbons,    -   and/or less than 2% by weight and preferably less than 1% by        weight of aromatic hydrocarbons,    -   and/or less than 2% by weight, preferably less than 1% by weight        and preferentially less than 0.1% by weight of unsaturated        hydrocarbons,    -   said percentages being expressed relative to the total weight of        the mixture.

More particularly, the volatile linear alkanes that are suitable for theinvention may be used in the form of an n-undecane/n-tridecane mixture.

In particular, use will be made of a mixture of volatile linear alkanescomprising:

-   -   from 55% to 80% by weight and preferably from 60% to 75% by        weight of C11 volatile linear alkane (n-undecane) and    -   from 20% to 45% by weight and preferably from 24% to 40% by        weight of C13 volatile linear alkane (n-tridecane),    -   relative to the total weight of the alkanes in said mixture.

According to one particular embodiment, the mixture of alkanes is ann-undecane/n-tridecane mixture. In particular, such a mixture may beobtained according to Example 1 or Example 2 of application WO 2008/155059.

According to another particular embodiment, the n-dodecane sold underthe reference Parafol 12-97 by Sasol is used.

According to another particular embodiment, the n-tetradecane sold underthe reference Parafol 14-97 by Sasol is used.

According to yet another embodiment, a mixture of n-dodecane andn-tetradecane is used

Among the animal oils, mention may be made of perhydrosqualene.

Among the triglycerides of plant or synthetic origin, mention may bemade of liquid fatty acid triglycerides comprising from 6 to 30 carbonatoms, for instance heptanoic or octanoic acid triglycerides, oralternatively, for example, sunflower oil, maize oil, soybean oil,marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil,macadamia oil, arara oil, castor oil, avocado oil, jojoba oil, sheabutter oil, caprylic/capric acid triglycerides, for instance those soldby the company Stéarineries Dubois or those sold under the namesMiglyol® 810, 812 and 818 by the company Dynamit Nobel.

Among the fluoro oils, mention may be made ofperfluoromethylcyclopentane and perfluoro-1,3-dimethylcyclohexane, soldunder the names Flutec® PC1 and Flutec® PC3 by the company BNFLFluorochemicals; perfluoro-1,2-dimethylcyclobutane; perfluoroalkanessuch as dodecafluoropentane and tetradecafluorohexane, sold under thenames PF 5050® and PF 5060® by the company 3M, or bromoperfluorooctylsold under the name Foralkyl® by the company Atochem;nonafluoromethoxybutane and nonafluoroethoxyisobutane;perfluoromorpholine derivatives such as 4-trifluoromethylperfluoromorpholine sold under the name PF 5052® by the company 3M.

The liquid fatty alcohols that may be used in the cosmetic compositionsof the invention are saturated or unsaturated, and linear or branched,and comprise from 6 to 30 carbon atoms and more particularly from 8 to30 carbon atoms. Examples that may be mentioned include cetyl alcohol,stearyl alcohol and the mixture thereof (cetylstearyl alcohol),octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol,oleyl alcohol and linoleyl alcohol.

The wax(es) which may be used in the cosmetic compositions of theinvention is (are) chosen in particular from carnauba wax, candelillawax, esparto grass wax, paraffin wax, ozokerite, plant waxes such asolive wax, rice wax, hydrogenated jojoba wax or the absolute waxes offlowers such as the essential wax of blackcurrant blossom sold by thecompany Bertin (France), animal waxes, for instance beeswaxes ormodified beeswaxes (cerabellina); other waxes or waxy starting materialsthat may be used according to the invention are in particular marinewaxes such as the product sold by the company Sophim under the referenceM82, and polyethylene waxes or polyolefin waxes in general.

As regards the fatty acid and/or fatty alcohol esters, which areadvantageously different from the triglycerides mentioned above, mentionmay be made in particular of esters of saturated or unsaturated, linearor branched C₁-C₂₆ aliphatic mono- or polyacids and of saturated orunsaturated, linear or branched C₁-C₂₆ aliphatic mono- or polyalcohols,the total carbon number of the esters more particularly being greaterthan or equal to 10.

Among the monoesters, mention may be made of dihydroabietyl behenate;octyldodecyl behenate; isocetyl behenate; cetyl lactate; C₁₂-C₁₅ alkyllactate; isostearyl lactate; lauryl lactate; linoleyl lactate; cetyllactate; (iso)stearyl octanoate; isocetyl octanoate; octyl octanoate;cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate;isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononylisononanoate; isostearyl palmitate; methylacetyl ricinoleate; myristylstearate; octyl isononanoate; 2-ethylhexyl isononate; octyl palmitate;octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate;ethyl and isopropyl palmitates, 2-ethylhexyl palmitate, 2-octyldecylpalmitate, alkyl myristates such as isopropyl, butyl, cetyl,2-octyldodecyl, myristyl or stearyl myristate, hexyl stearate, butylstearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyllaurate.

Still within the context of this variant, esters of C₄-C₂₂ dicarboxylicor tricarboxylic acids and of C₁-C₂₂ alcohols and esters of mono-, di-or tricarboxylic acids and of C₂C₂₆ di-, tri-, tetra- or pentahydroxyalcohols may also be used.

Mention may be made in particular of: diethyl sebacate; diisopropylsebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate;diisostearyl adipate; dioctyl maleate; glyceryl undecylenate;octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate;pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate;pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate;propylene glycol dicaprylate; propylene glycol dicaprate; tridecylerucate; triisopropyl citrate; triisostearyl citrate; glyceryltrilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleylcitrate; propylene glycol dioctanoate; neopentyl glycol diheptanoate;diethylene glycol diisononanoate; and polyethylene glycol distearates.

Among the esters mentioned above, it is preferred to use ethyl,isopropyl, myristyl, cetyl or stearyl palmitates, 2-ethylhexylpalmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl,butyl, cetyl or 2-octyldodecyl myristate, hexyl stearate, butylstearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyllaurate, isononyl isononanoate or cetyl octanoate.

The composition may also comprise, as fatty ester, sugar esters anddiesters of C₆-C₃₀ and preferably C₁₂-C₂₂ fatty acids. It is recalledthat the term “sugar” is intended to mean oxygen-bearinghydrocarbon-based compounds containing several alcohol functions, withor without aldehyde or ketone functions, and which comprise at least 4carbon atoms. These sugars may be monosaccharides, oligosaccharides orpolysaccharides.

Examples of suitable sugars that may be mentioned include sucrose (orsaccharose), glucose, galactose, ribose, fucose, maltose, fructose,mannose, arabinose, xylose and lactose, and derivatives thereof, inparticular alkyl derivatives, such as methyl derivatives, for instancemethylglucose.

The sugar esters of fatty acids may be chosen in particular from thegroup comprising the esters or mixtures of esters of sugars describedpreviously and of linear or branched, saturated or unsaturated C₆-C₃₀and preferably C₁₂-C₂₂ fatty acids. If they are unsaturated, thesecompounds may comprise one to three conjugated or non-conjugatedcarbon-carbon double bonds.

The esters according to this variant may also be chosen from monoesters,diesters, triesters, tetraesters and polyesters, and mixtures thereof.

These esters may be, for example, oleates, laurates, palmitates,myristates, behenates, cocoates, stearates, linoleates, linolenates,caprates or arachidonates, or mixtures thereof such as, in particular,oleate/palmitate, oleate/stearate or palmitate/stearate mixed esters.

More particularly, use is made of monoesters and diesters and inparticular mono- or di-oleate, -stearate, -behenate, -oleate/palmitate,-linoleate, -linolenate or -oleate/stearate of sucrose, glucose ormethylglucose.

An example that may be mentioned is the product sold under the nameGlucate® DO by the company Amerchol, which is a methylglucose dioleate.

Examples of esters or mixtures of esters of sugar of fatty acid that mayalso be mentioned include:

-   -   the products sold under the names F160, F140, F110, F90, F70 and        SL40 by the company Crodesta, respectively denoting sucrose        palmitate/stearates formed from 73% monoester and 27% diester        and triester, from 61% monoester and 39% diester, triester and        tetraester, from 52% monoester and 48% diester, triester and        tetraester, from 45% monoester and 55% diester, triester and        tetraester, from 39% monoester and 61% diester, triester and        tetraester, and sucrose monolaurate;    -   the products sold under the name Ryoto Sugar Esters, for example        referenced B370 and corresponding to sucrose behenate formed        from 20% monoester and 80% diester-triester-polyester;    -   the sucrose monopalmitate/stearate-dipalmitate/stearate sold by        the company Goldschmidt under the name Tegosoft® PSE.

The silicones that may be used in the cosmetic composition (A) of thepresent invention are volatile or non-volatile, cyclic, linear orbranched silicones, which are unmodified or modified with organicgroups, having a viscosity from 5×10⁻⁶ to 2.5 m²/s at 25° C., andpreferably 1×10⁻⁵ to 1 m²/s.

The silicones that may be used in accordance with the invention may bein the form of oils, waxes, resins or gums.

Preferably, the silicone is chosen from polydialkylsiloxanes, inparticular polydimethylsiloxanes (PDMSs), and organomodifiedpolysiloxanes comprising at least one functional group chosen frompoly(oxyalkylene) groups, amino groups and alkoxy groups.

Organopolysiloxanes are defined in greater detail in Walter Noll'sChemistry and Technology of Silicones (1968), Academic Press. They maybe volatile or nonvolatile.

When they are volatile, the silicones are more particularly chosen fromthose with a boiling point of between 60° C. and 260° C., and even moreparticularly from:

cyclic polydialkylsiloxanes containing from 3 to 7 and preferably from 4to 5 silicon atoms. These are, for example, octamethylcyclotetrasiloxanesold in particular under the name Volatile Silicone® 7207 by UnionCarbide or Silbione® 70045 V 2 by Rhodia, decamethylcyclopentasiloxanesold under the name Volatile Silicone® 7158 by Union Carbide, andSilbione® 70045 V 5 by Rhodia, and mixtures thereof.

Mention may also be made of cyclocopolymers of thedimethylsiloxane/methylalkylsiloxane type, such as Volatile Silicone® FZ3109 sold by the company Union Carbide, of formula:

Mention may also be made of mixtures of cyclic polydialkylsiloxanes withorganosilicon compounds, such as the mixture ofoctamethylcyclotetrasiloxane and tetra(trimethylsilyl)pentaerythritol(50/50) and the mixture of octamethylcyclotetrasiloxane andoxy-1,1′-bis(2,2,2′,2′,3,3′-hexatrimethylsilyloxy)neopentane; (ii)linear volatile polydialkylsiloxanes containing 2 to 9 silicon atoms andhaving a viscosity of less than or equal to 5×10⁻⁶ m²/s at 25° C. Anexample is decamethyltetrasiloxane sold in particular under the name SH200 by the company Toray Silicone. Silicones belonging to this categoryare also described in the article published in Cosmetics and Toiletries,Vol. 91, January 76, pp. 27-32, Todd & Byers, Volatile Silicone Fluidsfor Cosmetics.

Use is preferably made of non-volatile polydialkylsiloxanes,polydialkylsiloxane gums and resins, polyorganosiloxanes modified withthe organofunctional groups above, and mixtures thereof.

These silicones are more particularly chosen from polydialkylsiloxanes,among which mention may be made mainly of polydimethylsiloxanes havingtrimethylsilyl end groups. The viscosity of the silicones is measured at25° C. according to ASTM Standard 445 Appendix C.

Among these polydialkylsiloxanes, mention may be made, in a nonlimitingmanner, of the following commercial products:

-   -   the Silbione® oils of the 47 and 70 047 series or the Mirasil®        oils sold by Rhodia, for instance the oil 70 047 V 500 000;    -   the oils of the Mirasil® series sold by the company Rhodia;    -   the oils of the 200 series from the company Dow Corning, such as        DC200 with a viscosity of 60 000 mm²/s;    -   the Viscasil® oils from General Electric and certain oils of the        SF series (SF 96, SF 18) from General Electric.

Mention may also be made of polydimethylsiloxanes bearingdimethylsilanol end groups known under the name dimethiconol (CTFA),such as the oils of the 48 series from the company Rhodia.

In this category of polydialkylsiloxanes, mention may also be made ofthe products sold under the names Abil Wax® 9800 and 9801 by the companyGoldschmidt, which are poly(C₁-C₂₀)dialkylsiloxanes.

The silicone gums that may be used in accordance with the invention arein particular polydialkylsiloxanes and preferably polydimethylsiloxaneswith high number-average molecular weights of between 200 000 and 1 000000, used alone or as a mixture in a solvent. This solvent can be chosenfrom volatile silicones, polydimethylsiloxane (PDMS) oils,polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes,methylene chloride, pentane, dodecane and tridecane, or mixturesthereof.

Products that can be used more particularly in accordance with theinvention are mixtures such as:

-   -   mixtures formed from a hydroxy-terminated polydimethylsiloxane        or dimethiconol (CTFA), and from a cyclic polydimethylsiloxane,        also known as cyclomethicone (CTFA), such as the product Q2 1401        sold by the company Dow Corning;    -   mixtures of a polydimethylsiloxane gum and a cyclic silicone,        such as the product SF 1214 Silicone Fluid from the company        General Electric; this product is an SF 30 gum corresponding to        a dimethicone, having a number-average molecular weight of 500        000, dissolved in the oil SF 1202 Silicone Fluid corresponding        to decamethylcyclopentasiloxane;    -   mixtures of two PDMSs with different viscosities, and more        particularly of a PDMS gum and of a PDMS oil, such as the        product SF 1236 from the company General Electric. The product        SF 1236 is a mixture of a gum SE 30 defined above with a        viscosity of 20 m²/s and of an oil SF 96 with a viscosity of        5×10⁻⁶ m²/s. This product preferably comprises 15% of gum SE 30        and 85% of an oil SF 96.

The organopolysiloxane resins that may be used in accordance with theinvention are crosslinked siloxane systems containing the followingunits:

R₂SiO_(2/2), R₃SiO_(1/2), RSiO_(3/2) and SiO_(4/2).

in which R represents an alkyl containing 1 to 16 carbon atoms. Amongthese products, the ones that are particularly preferred are those inwhich R denotes a C₁-C₄ lower alkyl group, more particularly methyl.

Among these resins, mention may be made of the product sold under thename Dow Corning 593 or those sold under the names Silicone Fluid SS4230 and SS 4267 by the company General Electric, and which aresilicones of dimethyl/trimethylsiloxane structure. Mention may also bemade of the trimethyl siloxysilicate-type resins sold in particularunder the names X22-4914, X21-5034 and X21-5037 by the companyShin-Etsu.

The organomodified silicones that may be used in accordance with theinvention are silicones as defined previously and comprising in theirstructure one or more organofunctional groups attached via ahydrocarbon-based group.

Besides the silicones described above, the organomodified silicones maybe polydiarylsiloxanes, in particular polydiphenylsiloxanes, andpolyalkylarylsiloxanes functionalized by the organofunctional groupsmentioned previously.

The polyalkylarylsiloxanes are particularly chosen from linear and/orbranched polydimethyl/methylphenylsiloxanes andpolydimethyl/diphenylsiloxanes with a viscosity ranging from 1×10⁻⁵ to5×10⁻² m²/s at 25° C.

Among these polyalkylarylsiloxanes, examples that may be mentionedinclude the products sold under the following names:

-   -   the Silbione® oils of the 70 641 series from Rhodia;    -   the oils of the Rhodorsil® 70 633 and 763 series from Rhodia;    -   the oil Dow Corning 556 Cosmetic Grade Fluid from Dow Corning;    -   the silicones of the PK series from Bayer, such as the product        PK20;    -   the silicones of the PN and PH series from Bayer, such as the        products PN1000 and PH1000;    -   certain oils of the SF series from General Electric, such as SF        1023, SF 1154, SF 1250 and SF 1265.

Among the organomodified silicones, mention may be made ofpolyorganosiloxanes comprising:

-   -   polyethyleneoxy and/or polypropyleneoxy groups optionally        comprising C₆-C₂₄ alkyl groups, such as the products known as        dimethicone copolyol sold by the company Dow Corning under the        name DC 1248 or the oils Silwet® L 722, L 7500, L 77 and L 711        by the company Union Carbide, and the (C₁₂)alkylmethicone        copolyol sold by the company Dow Corning under the name Q2 5200;    -   substituted or unsubstituted amine groups, such as the products        sold under the names GP 4 Silicone Fluid and GP 7100 by the        company Genesee or the products sold under the names Q2 8220 and        Dow Corning 929 or 939 by the company Dow Corning. The        substituted amine groups are, in particular, C₁-C₄ aminoalkyl        groups;    -   alkoxy groups such as the product sold under the name Silicone        Copolymer F-755 by SWS Silicones, and Abil Wax® 2428, 2434 and        2440 by the company Goldschmidt. Preferably, the fatty        substances do not comprise any C₂-C₃ oxyalkylene units or any        glycerol units. Preferably, the fatty substances are not fatty        acids and in particular salified fatty acids or soaps which are        water-soluble compounds.

The fatty substances are advantageously chosen from C₆-C₁₆ hydrocarbonsor hydrocarbons comprising more than 16 carbon atoms, and in particularalkanes, oils of plant origin, fatty alcohols, fatty acid and/or fattyalcohol esters, and silicones, or mixtures thereof.

Preferably, the fatty substance is an oil (a compound that is liquid ata temperature of 25° C. and at atmospheric pressure).

Preferably, the fatty substance is chosen from liquid petroleum jelly,C₆-C₁₆ alkanes, volatile linear alkanes, polydecenes, liquid fatty acidand/or fatty alcohol esters, and liquid fatty alcohols, or mixturesthereof. Better still, the fatty substance is chosen from liquidpetroleum jelly, C₆-C₁₆ alkanes and polydecenes.

The fatty substances are present in a content of greater than 10% byweight, relative to the total weight of the cosmetic composition (B).

The composition (B) has a fatty substance content preferably rangingfrom 10% to 80% by weight, and even more particularly ranging from 20%to 75% by weight, better still from 25% to 70% by weight and quiteparticularly from 40% to 60% by weight relative to the total weight ofthe composition (B); preferentially, from 50% to 80% by weight relativeto the total weight of the composition (B).

According to one advantageous variant of the invention, the process ofthe invention uses the composition (A) which has a fatty substancecontent preferably ranging from 10% to 90% by weight, and even moreparticularly from 20% to 80% by weight, better still from 20% to 50% byweight, relative to the total weight of the composition (A).

ii) Metal Catalyst(s)

The dyeing process according to the present invention uses in itscomposition (B) one or more metal catalysts.

Metal catalysts are compounds which comprise one or more metals in theirstructure.

The metals are chosen from transition metals and rare earth metals, andalloys thereof.

In particular, the metals are chosen from transition metals and rareearth metals.

Among the transition metals, mention may in particular be made ofmanganese, iron, cobalt, copper, zinc, platinum, nickel, titanium,silver, zirconium, chromium, molybdenum, tungsten, gold and vanadium,and among said metals, quite particularly manganese.

Among the transition metals, mention is preferably made of manganese,iron, cobalt, zinc, platinum, nickel, titanium, silver, zirconium,chromium, molybdenum, tungsten, gold and vanadium, and among saidmetals, quite preferably manganese.

Among the rare earth metals, mention may particularly be made of cerium.

Thus, the metal catalysts are in particular catalysts based ontransition metals or on rare earth metals, and more particularlymagnesium-based, vanadium-based or cerium-based catalysts.

The metal catalysts used may be chosen from metal salts, metal oxidesand metal complexes, and mixtures thereof.

For the purposes of the present invention, the term “metal complexes” isintended to mean systems in which the metal ion, i.e. the central atom,is bonded to one or more electron donors, called ligands, via chemicalbonds. As an example, mentioned may be made of porphyrins andphthalocyanines, which are in particular cationic.

Preferably, the metal catalysts used in the dyeing process are chosenfrom metal salts.

For the purposes of the present invention, the term “metal salts” isintended to mean the salts derived from the action of an acid on ametal.

Preferentially, the metal catalysts used in the dyeing process arechosen from transition metal salts, such as manganese salts, and rareearth metal salts, such as cerium salts, and also mixtures thereof.

The metal salts may be inorganic or organic salts.

According to one variant, the metal salts are inorganic and may bechosen from halides, carbonates, sulfates and phosphates, in particularoptionally hydrated halides.

According to another preferred variant, the metal salts are in oxidationstate II and have two (poly)hydroxy acid-derived ligands.

The term “(poly)hydroxy acid” is intended to mean any carboxylic acidwhich comprises a hydrocarbon-based chain which is linear or branched,and saturated or unsaturated, preferably saturated and/or linear,comprising from 1 to 10 carbon atoms and from 1 to 9 hydroxyl groups,and comprising from 1 to 4 carboxylic groups —C(O)—OH, at least one ofsaid —C(O)—OH functions of which is in the carboxylate form —C(O)—O⁻complexed with the metal atom, preferably Mn(II). More particularly, themetal salt is complexed with two carboxylate groups such as that offormula (I):

R—C(O)—O—M—O—C(O)—R′  (I)

and also the solvates thereof, such as the hydrates, and the enantiomersthereof, in which formula (I):

-   -   M represents a metal (II) or metal²⁺ in oxidation state 2,    -   R and R′, which may be identical or different, represent a        (C₁-C₆)(poly)hydroxyalkyl group. The metal catalysts are        particularly chosen from organic acid salts of transition        metals, in particular of manganese, and inorganic salts of rare        earth metals, in particular of cerium.

According to one particular embodiment of the invention, the manganeseis not a manganese oxide, but a manganese salt

The organic metal salts may be more particularly chosen from organicacid salts such as citrates, lactates, glycolates, gluconates, acetates,propionates, fumarates, oxalates and tartrates, in particulargluconates.

More preferentially, the metal catalysts are manganese gluconate andcerium chloride heptahydrate, in particular manganese gluconate.

Preferably, the metal catalyst(s) is (are) chosen from the compounds offormula (I) and more particularly represent(s) manganese gluconate.

The metal catalysts, when they are in the form of composition (B), maybe present in a content ranging from 0.001% to 10% by weight, preferablyin a content ranging from 0.001% to 1% by weight, better still rangingfrom 0.01% to 0.5% by weight relative to the total weight of thecomposition (B).

The composition (B) may exclusively contain the metal catalyst(s)combined with one or more fatty substances. According to anothervariant, this composition (B) contains compounds other than the metalcatalyst(s), such as the additional ingredients, see “Additionalingredients or adjuvants” below.

This composition (B) may be anhydrous or aqueous, preferably aqueous.

The composition (A) used in the invention is a ready-to-use compositionand comprises i) at least one oxidation base; ii) optionally at leastone coupler; iii) at least one chemical oxidizing agent; and iv)optionally at least one organic or inorganic alkaline agent. Thecomposition (A′) of the device of the invention comprises the oxidationdyes i) and ii) as previously defined.

Oxidation Bases:

According to one particular embodiment of the invention, the oxidationbase(s) is (are) preferably chosen from para-phenylenediamines,bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols,heterocyclic bases preferably comprising at least two nitrogen atoms,and addition salts thereof and/or solvates thereof; preferably theoxidation base(s) is (are) chosen from para-phenylenediamines,bis(phenyl)alkylenediamines.

Among the para-phenylenediamines that may be mentioned, for example, arepara-phenylenediamine, para-toluenediamine,2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine,N,N-diethyl-para-phenylenediamine, N, N-dipropyl-para-phenylenediamine,4-amino-N,N-diethyl-3-methylaniline,N,N-bis((3-hydroxyethyl)-para-phenylenediamine,4-N,N-bis((3-hydroxyethyl)amino-2-methylaniline,4-N,N-bis((3-hydroxyethyl)amino-2-chloroaniline,2-8-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine,2-isopropyl-para-phenylenediamine,N-((3-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylenediamine,N,N-dimethyl-3-methyl-para-phenylenediamine,N,N-(ethyl-(3-hydroxyethyl)-para-phenylenediamine,N-β,γ-dihydroxypropyl)-para-phenylenediamine,N-(4′-aminophenyl)-para-phenylenediamine,N-phenyl-para-phenylenediamine,2-β-hydroxyethyloxy-para-phenylenediamine,2-β-acetylaminoethyloxy-para-phenylenediamine,N-(β-methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine,2-thienyl-para-phenylenediamine, 2-β-hydroxyethylamino-5-aminotolueneand 3-hydroxy-1-(4′-aminophenyl)pyrrolidine, and the addition saltsthereof with an acid.

Preference is particularly given, among the abovementionedpara-phenylenediamines, to para-phenylenediamine, para-toluylenediamine,2-isopropyl-para-phenylenediamine,2-(β-hydroxyethyl)-para-phenylenediamine,2-(β-hydroxyethyloxy)-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,2-chloro-para-phenylenediamine,2-(β-acetylaminoethyloxy)-para-phenylenediamine and the addition saltsthereof with an acid.

Among the bis(phenyl)alkylenediamines, examples that may be mentionedincludeN,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)1,3-diaminopropanol,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenypethylenediamine,N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(4-methylaminophenyl)tetramethylenediamine,N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine,1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane and the addition saltsthereof.

Among the para-aminophenols that may be mentioned, for example, arepara-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol,4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol,4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol,4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol,4-amino-2-(β-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol,and the addition salts thereof with an acid.

Among the ortho-aminophenols that may be mentioned, for example, are2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and5-acetamido-2-aminophenol, and the addition salts thereof.

Among the heterocyclic bases, preference is given to those comprising atleast two nitrogen atoms. More particularly, pyridine derivatives,pyrimidine derivatives and pyrazole derivatives are preferred.

Among the pyridine derivatives, examples that may be mentioned includethe compounds described in patents GB 1 026 978 and GB 1 153 196, forinstance 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridineand 3,4-diaminopyridine, and the addition salts thereof.

Other pyridine oxidation bases that are useful in the present inventionare the 3-aminopyrazolo[1,5-a]pyridine oxidation bases or the additionsalts thereof, described, for example, in patent application FR 2 801308. Examples that may be mentioned includepyrazolo[1,5-a]pyrid-3-ylamine,2-acetylaminopyrazolo[1,5-a]pyrid-3-ylamine,2-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine,3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid,2-methoxypyrazolo[1,5-a]pyrid-3-ylamine,(3-aminopyrazolo[1,5-a]pyrid-7-yl)methanol,2-(3-aminopyrazolo[1,5-a]pyrid-5-yl)ethanol,2-(3-aminopyrazolo[1,5-a]pyrid-7-yl)ethanol,(3-aminopyrazolo[1,5-a]pyrid-2-yl)methanol,3,6-diaminopyrazolo[1,5-a]pyridine, 3,4-diaminopyrazolo[1,5-a]pyridine,pyrazolo[1,5-a]pyridine-3,7-diamine,7-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine,pyrazolo[1,5-a]pyridine-3,5-diamine,5-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine,2-[(3-aminopyrazolo[1,5-a]pyrid-5-yl)(2-hydroxyethy)amino]ethanol,2-[(3-aminopyrazolo[1,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol,3-aminopyrazolo[1,5-a]pyridin-5-ol, 3-aminopyrazolo[1,5-a]pyridin-4-ol,3-aminopyrazolo[1,5-a]pyridin-6-ol, 3-aminopyrazolo[1,5-a]pyridin-7-ol,2-(2-hydroxyethoxy)-3-aminopyrazolo[1,5-a]pyridine,2-(4-methylpiperazinium-1-yl)-3-aminopyrazolo[1,5-a]pyridine, and theaddition salts thereof.

Among the pyrimidine derivatives, mention may be made of the compoundsdescribed, for example, in patents DE 2359399, JP 88-169571, JP 05-63124and EP 0 770 375 or patent application WO 96/15765, such as2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine,2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine,2,5,6-triaminopyrimidine and the addition salts thereof, and thetautomeric forms thereof, when a tautomeric equilibrium exists.

Among the pyrazole derivatives, mention may be made of the compoundsdescribed in patents DE 3843892, DE 4133957 and patent applications WO94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, such as4,5-diamino-1-methylpyrazole, 4,5-diamino-1-β-hydroxyethyl)pyrazole,3,4-diaminopyrazole, 4,5-diamino-1-(4′-chlorobenzyl)pyrazole,4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole,4,5-diamino-1-methyl-3-phenylpyrazole,4-amino-1,3-dimethyl-5-hydrazinopyrazole,1-benzyl-4,5-diamino-3-methylpyrazole,4,5-diamino-3-tert-butyl-1-methylpyrazole,4,5-diamino-1-tert-butyl-3-methylpyrazole,4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole,4,5-diamino-1-ethyl-3-methylpyrazole,4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole,4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,4,5-diamino-3-hydroxymethyl-1-methylpyrazole,4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,4,5-diamino-3-methyl-1-isopropylpyrazole,4-amino-5-(2′-aminoethyl)amino-1,3-dimethylpyrazole,3,4,5-triamino-pyrazole, 1-methyl-3,4,5-triaminopyrazole,3,5-diamino-1-methyl-4-methylaminopyrazole,3,5-diamino-4-(β-hydroxyethypamino-1-methylpyrazole, and the additionsalts thereof. Use may also be made of4,5-diamino-1-(β-methoxyethy)pyrazole.

A 4,5-diaminopyrazole and even more preferentially4,5-diamino-1-(β-hydroxyethyl)pyrazole and/or a salt thereof willpreferably be used.

Pyrazole derivatives that may also be mentioned includediamino-N,N-dihydropyrazolopyrazolones and in particular those describedin application FR-A-2 886 136, such as the following compounds and theaddition salts thereof:2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-isopropylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,4,5-diamino-1,2-dimethyl-1,2-dihydropyrazol-3-one,4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one,4,5-diamino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one,2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyridazino[1,2-a]pyrazol-1-one,4-amino-1,2-diethyl-5-(pyrrolidin-1-yl)-1,2-dihydropyrazol-3-one,4-amino-5-(3-dimethylaminopyrrolidin-1-yl)-1,2-diethyl-1,2-dihydropyrazol-3-oneor 2,3-diamino-6-hydroxy-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one.

Use will preferably be made of2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or a saltthereof.

As heterocyclic bases, use will preferentially be made of4,5-diamino-1-(β-hydroxyethyl)pyrazole,2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-(2-hydroxyethoxy)-3-aminopyrazolo[1,5-a]pyridine and2-(4-methylpiperazinium-1-yl)-3-aminopyrazolo[1,5-a]pyridine; and/or anaddition salt thereof.

Couplers:

According to one particular embodiment of the invention, the composition(C) comprises one or more couplers that are conventionally used fordyeing keratin fibres.

Preferably, the couplers are chosen from meta-phenylenediamines,meta-aminophenols, meta-diphenols, naphthalene-based couplers andheterocyclic couplers, and also the addition salts thereof.

Examples that may be mentioned include 1,3-dihydroxybenzene,1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene,2,4-diamino-1-(β-hydroxyethyloxy)benzene,2-amino-4-(6-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene,1,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline,3-ureido-1-dimethylaminobenzene, sesamol,1-6-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol,2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole,4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine,6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine,1-N-(6-hydroxyethyl)amino-3,4-methylenedioxybenzene,2,6-bis(6-hydroxyethylamino)toluene, 6-hydroxyindoline,2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one,1-phenyl-3-methylpyrazol-5-one,2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,2,6-dimethyl[3,2-c]-1,2,4-triazole and6-methylpyrazolo[1,5-a]benzimidazole, the addition salts thereof with anacid, and mixtures thereof.

In general, the addition salts of the oxidation bases and couplers thatmay be used in the context of the invention are in particular chosenfrom the addition salts with an acid, such as hydrochlorides,hydrobromides, sulfates, citrates, succinates, tartrates, lactates,tosylates, benzenesulfonates, phosphates and acetates.

The oxidation base(s) each advantageously represent from 0.001% to 10%by weight, and preferably from 0.005% to 5% by weight relative to thetotal weight of the composition (A′) and of the ready-to-use composition(A).

The content of coupler(s), if it (they) is (are) present, eachadvantageously represent from 0.001% to 10% by weight relative to thetotal weight of the composition, and preferably from 0.005% to 5% byweight relative to the total weight of the composition (A′) and of theready-to-use composition (A).

According to one particular embodiment of the invention, the composition(A) as previously defined also comprises one or more synthetic ornatural direct dyes, chosen from ionic or non-ionic species, preferablycationic or non-ionic species, either as sole dyes or in addition to theoxidation dye(s).

Examples of suitable direct dyes that may be mentioned include azodirect dyes; (poly)methine dyes such as cyanins, hemicyanins andstyryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes;tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanin dyes, andnatural direct dyes, alone or as mixtures.

Mention may be made, among the natural direct dyes which can be usedaccording to the invention, of lawsone, juglone, alizarin, purpurin,carminic acid, kermesic acid, purpurogallin, protocatechualdehyde,indigo, isatin, curcumin, spinulosin, apigenidin and orceins. Extractsor decoctions containing these natural dyes, and in particularhenna-based poultices or extracts, may also be used.

When they are present, the direct dye(s) more particularly represent(s)from 0.001% to 10% by weight and preferably from 0.005% to 5% by weightrelative to the total weight of the composition (A′) or of thecomposition (A).

Chemical Oxidizing Agents:

More particularly, the chemical oxidizing agent(s) are chosen fromhydrogen peroxide, urea peroxide, alkali metal bromates orferricyanides, peroxygenated salts, for instance alkali metal oralkaline-earth metal persulfates, perborates, peracids and precursorsthereof and percarbonates, and peracids and precursors thereof.

The oxidizing agent is preferably hydrogen peroxide.

This oxidizing agent advantageously consists of hydrogen peroxide, theconcentration of which can range, more particularly from 0.1% to 50% byweight, more preferably still from 0.5% to 20% by weight and betterstill from 1% to 15% by weight, relative to the composition (C) or (D).

Additional Ingredients or Adjuvants:

According to one particular embodiment, the compositions (A), (A′), (B),(C) and/or (D) comprise one or more non-ionic, preferablyoxyalkylenated, surfactants.

In accordance with one preferred embodiment of the invention, thesurfactants are oxyalkylenated non-ionic surfactants and are chosen fromoxyethylenated C₈-C₃₀ alcohols, and polyoxyethylenated esters ofsaturated or unsaturated, linear or branched C₈-C₃₀ acids and ofsorbitol.

Preferably, the cosmetic compositions (A) and/or (C) comprise one ormore non-ionic surfactants.

The surfactant content in the compositions (A) and/or (C) representsmore particularly from 0.1% to 50% by weight and preferably from 0.5% to30% by weight, relative to the weight of the composition underconsideration.

The compositions (A), (B), (C) and/or (D) may also contain variousadjuvants conventionally used in hair dyeing compositions, such asanionic, cationic, nonionic, amphoteric or zwitterionic polymers ormixtures thereof; inorganic thickeners, and in particular fillers suchas clays or talc; organic thickeners/gelling agents with, in particular,anionic, cationic, nonionic and amphoteric polymeric associativethickeners other than the polymers previously mentioned; antioxidants;penetrants; sequestrants; fragrances; dispersants; film-forming agents;ceramides; preserving agents; opacifiers.

The above adjuvants are generally present in an amount for each of themof between 0.01% and 20% by weight relative to the weight of thecomposition under consideration.

According to one advantageous variant of the invention, the anhydrouscomposition (A) comprises one or more inorganic thickeners chosen fromorganophilic clays.

The organophilic clay can be chosen from montmorillonite, bentonite,hectorite, attapulgite, sepiolite and mixtures thereof. The clay ispreferably a bentonite or a hectorite.

These clays can be modified with a chemical compound chosen fromquaternary amines, tertiary amines, amine acetates, imidazolines, aminesoaps, fatty sulfates, alkylarylsulfonates and amine oxides, andmixtures thereof.

Mention may be made, as organophilic clays, of quaternium-18 bentonites,such as those sold under the names Bentone 3, Bentone 38 and Bentone 38Vby the company Rheox, Tixogel VP by the company United Catalyst andClaytone 34, Claytone 40 and Claytone XL by the company Southern Clay;stearalkonium bentonites, such as those sold under the names Bentone 27by the company Rheox, Tixogel LG by the company United Catalyst andClaytone AF and Claytone APA by the company Southern Clay;quaternium-18/benzalkonium bentonites, such as those sold under thenames Claytone HT and Claytone PS by the company Southern Clay;quaternium-18 hectorites, such as those sold under the names Bentone GelDOA, Bentone Gel ECO5, Bentone Gel EUG, Bentone Gel IPP, Bentone GelISD, Bentone Gel SS71, Bentone Gel VS8 and Bentone Gel VS38 by thecompany Rheox, and Simagel M and Simagel SI 345 by the company Biophil.

When it is present, the inorganic thickener represents from 0.5% to 30%by weight relative to the weight of the composition. Advantageously, thecomposition is in the form of a gel, a cream or a foam.

The compositions (B) and/or (A) may be anhydrous or aqueous.

More particularly, for the purposes of the invention, the expression“anhydrous cosmetic composition” is intended to mean a cosmeticcomposition with a water content of less than 5% by weight, preferablyless than 2% by weight and more preferably still less than 1% by weightrelative to the weight of said composition. It should be noted that thewater in question is more particularly bound water, such as water ofcrystallization in salts, or traces of water absorbed by the rawmaterials used in the production of the compositions according to theinvention.

The term “aqueous composition” is intended to mean a compositioncomprising more than 5% by weight of water, preferably more than 10% byweight of water and more advantageously still more than 20% by weight ofwater.

Preferably, the cosmetic compositions (A) and/or (B) are aqueouscompositions.

More preferentially still, the water concentration of the composition(A) or (B) may range from 10% to 90% and better still from 20% to 80% ofthe total weight of the composition.

The compositions (A), (A′), (B), (C) and/or (D) may optionally compriseone or more organic solvents.

Examples of organic solvents that may be mentioned include linear orbranched C₂-C₄ alkanols, such as ethanol and isopropanol; glycerol;polyols and polyol ethers, for instance 2-butoxyethanol, propyleneglycol, dipropylene glycol, propylene glycol monomethyl ether,diethylene glycol monomethyl ether and monoethyl ether, and alsoaromatic alcohols, for instance benzyl alcohol or phenoxyethanol, andmixtures thereof.

The organic solvent(s), if it (they) is (are) present, represent(s) acontent usually ranging from 1% to 40% and preferably ranging from 5% to30% by weight relative to the weight of the composition containing it(them).

The pH of the compositions (A), (A′), (B), (C) and/or (D), if they areaqueous, ranges from 2 to 13.

For the compositions (A) and (B), the pH preferably ranges from 6.5 to12 and better still from 8 to 12. The pH is adjusted using additionalacidifying or alkaline agents, such as those mentioned below.

Basifying Agents:

Preferably, the compositions (A) and/or (B) comprise one or more organicor inorganic, preferably organic, basifying agents.

The basifying agent(s) can be inorganic or organic.

The inorganic basifying agent(s) is (are) preferably chosen from aqueousammonia, alkali metal carbonates or bicarbonates such as sodiumcarbonate, potassium carbonate, sodium bicarbonate or potassiumbicarbonate, sodium hydroxide or potassium hydroxide, or mixturesthereof.

The organic basifying agent(s) are preferably chosen from organic amineswith a pK_(b) at 25° C. of less than 12, preferably less than 10 andeven more advantageously less than 6.

It should be noted that it is the pK_(b) corresponding to the functionof highest basicity. In addition, the organic amines do not comprise anyalkyl or alkenyl fatty chains comprising more than ten carbon atoms.

The organic basifying agent(s) is (are) chosen, for example, fromalkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines,amino acids and the compounds of formula (III) below:

in which formula (III) W is a divalent C₁-C₆ alkylene radical optionallysubstituted with one or more hydroxyl groups or a C₁-C₆ alkyl radical,and/or optionally interrupted with one or more heteroatoms such as O, orNR_(u), and R_(x), R_(y), R_(z), R_(t) and R_(u), which may be identicalor different, represent a hydrogen atom or a C₁-C₆ alkyl, C₁-C₆hydroxyalkyl or C₁-C₆ aminoalkyl radical.

Examples of amines of formula (III) that may be mentioned include1,3-diaminopropane, 1,3-diamino-2-propanol, spermine and spermidine.

The term “alkanolamine” is intended to mean an organic amine comprisinga primary, secondary or tertiary amine function, and one or more linearor branched C₁-C₈ alkyl groups bearing one or more hydroxyl radicals.

The organic amines chosen from alkanolamines such as monoalkanolamines,dialkanolamines or trialkanolamines comprising one to three identical ordifferent C₁-C₄ hydroxyalkyl radicals are in particular suitable forcarrying out the invention.

Among the compounds of this type, mention may be made ofmonoethanolamine (MEA), diethanolamine, triethanolamine,monoisopropanolamine, diisopropanolamine, N,N-dimethylethanolamine,2-amino-2-methyl-1-propanol, triisopropanolamine,2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol,3-dimethylamino-1,2-propanediol and tris(hydroxymethyl)aminomethane.

More particularly, the amino acids that can be used are of natural orsynthetic origin, in their L, D or racemic form, and comprise at leastone acid function chosen more particularly from carboxylic acid,sulfonic acid, phosphonic acid or phosphoric acid functions. The aminoacids may be in neutral or ionic form.

As amino acids that can be used in the present invention, mention may bemade in particular of aspartic acid, glutamic acid, alanine, arginine,ornithine, citrulline, asparagine, carnitine, cysteine, glutamine,glycine, histidine, lysine, isoleucine, leucine, methionine,N-phenylalanine, proline, serine, taurine, threonine, tryptophan,tyrosine and valine.

Advantageously, the amino acids are basic amino acids comprising anadditional amine function optionally included in a ring or in a ureidofunction.

Such basic amino acids are preferably chosen from those corresponding toformula (IV) below, and also the salts thereof:

in which formula (IV) R represents a group chosen from:

The compounds corresponding to the formula (IV) are histidine, lysine,arginine, ornithine and citrulline.

The organic amine may also be chosen from organic amines of heterocyclictype. Besides histidine that has already been mentioned in the aminoacids, mention may in particular be made of pyridine, piperidine,imidazole, triazole, tetrazole and benzimidazole.

The organic amine may also be chosen from amino acid dipeptides. Asamino acid dipeptides that can be used in the present invention, mentionmay be made in particular of carnosine, anserine and balenine.

The organic amine may also be chosen from compounds comprising aguanidine function. As amines of this type that can be used in thepresent invention, besides arginine, which has already been mentioned asan amino acid, mention may be made in particular of creatine,creatinine, 1,1-dimethylguanidine, 1,1-diethylguanidine, glycocyamine,metformin, agmatine, N-amidinoalanine, 3-guanidinopropionic acid,4-guanidinobutyric acid and2-([amino(imino)methyl]amino)ethane-1-sulfonic acid.

Hybrid compounds that may be mentioned include the salts of the aminesmentioned previously with acids such as carbonic acid or hydrochloricacid.

Guanidine carbonate or monoethanolamine hydrochloride may be used inparticular.

Preferably, the basifying agent(s) present in the composition of theinvention is (are) chosen from aqueous ammonia, alkanolamines, aminoacids in neutral or ionic form, in particular basic amino acids, andpreferably corresponding to those of formula (III).

Even more preferentially, the basifying agent(s) is (are) chosen fromaqueous ammonia and alkanolamines, most particularly monoethanolamine(MEA).

Better still, the basifying agent(s) is (are) chosen from alkanolamines,most particularly monoethanolamine (MEA).

By way of example, mention may be made of inorganic amines such asaqueous ammonia or organic amines. Organic amines chosen fromalkanolamines such as monoalkanolamines, dialkanolamines ortrialkanolamines comprising one to three identical or different C₁-C₄hydroxyalkyl radicals, in particular monoethanolamine, are particularlysuitable.

Preparation of the Ready-to-Use Composition (C):

As previously indicated, the ready-to-use composition (A) may resultfrom the mixing of a composition (A′) comprising i) one or moreoxidation bases, ii) optionally one or more couplers, and of acomposition (C) comprising one or more oxidizing agents as previouslydefined. The compositions (A′) and (C) are preferably aqueous. They mayin particular be in the form of direct or inverse emulsions.

They may also result from the mixing of three compositions, the firsttwo being the compositions (A′) and (C) above and the third compositionbeing a composition (D) comprising at least one fatty substance aspreviously defined.

This composition (D) may be anhydrous or aqueous. It is preferablyanhydrous.

Usually, the pH of the oxidizing composition (C), when it is aqueous, isacidic, i.e. less than 7.

Dyeing Processes:

In accordance with a first variant of the present invention, thecomposition (B) is applied to dry or wet keratin fibres. Then a dyeingcomposition (A) as previously defined is applied. According to onevariant, the compositions (A′) and (C) are mixed in order to produce theready-to-use composition (A), then the mixture produced is applied todry or wet keratin fibres.

There is preferably no intermediate rinsing.

The leave-on time of the composition (B) on the keratin fibres may rangefrom 1 to 60 minutes, and is preferably from 10 minutes to 20 minutes.

In particular, the composition (B) is applied to the keratin fibres andleft on for 10 minutes at ambient temperature.

Preferably, the composition (B) is sprayed onto the keratin fibres.

In addition, the dyeing composition (A) may be left in place on thekeratin fibres for a time generally of about from 1 minute to 1 hour,preferably from 5 minutes to 40 minutes and preferably for 35 minutes.

The temperature during the process is conventionally between ambienttemperature (between 15 and 25° C.) and 120° C. if a straightening ironis used, preferably between ambient temperature and 80° C., preferablyfrom ambient temperature to 60° C. and better still from ambienttemperature to 40° C.

According to one preferred embodiment, the composition (B) is applied towet or dry keratin fibres, then the fibres are rinsed and rubbed drywith a towel. The composition (A) as previously defined is then applied,and then said fibres are optionally washed, rinsed and/or dried.

The drying step may last from 5 to 20 minutes, preferably from 5 to 15minutes, and in particular lasts 10 minutes.

After the treatment, i.e. after the application of the composition (A)as previously defined, the human keratin fibres are preferably rinsedwith water, optionally washed with a shampoo and then rinsed with water,before being dried under a hood at a temperature ranging from 50 to 80°C., or left to dry.

According to one particular embodiment of the invention, the process fordyeing keratin fibres is carried out in at least three successive steps:

-   -   firstly, of a composition (B) as previously defined        comprising i) one or more metal catalysts chosen from transition        metal salts, in particular organic acid salts of transition        metals, and rare earth metal salts, in particular inorganic        salts of rare earth metals, preferably manganese salts; ii) at        least 10% preferably at least 35% of fatty substance(s), the        fatty substance(s) preferentially being chosen from fatty        substances that are liquid at ambient temperature and at        atmospheric pressure, in particular chosen from liquid petroleum        jelly, C₆-C₁₆ alkanes, polydecenes, liquid fatty acid and/or        fatty alcohol esters, liquid fatty alcohols, or mixtures        thereof;    -   and optionally iii) at least one basifying agent, in particular        chosen from alkanolamines such as triethanolamine;    -   then, secondly, intermediate rinsing, and optionally rubbing dry        preferably with a cloth or an absorbent paper,    -   then, thirdly, a ready-to-use cosmetic composition (A)        comprising i) at least one oxidation base chosen from        para-phenylenediamines, bis(phenyl)alkylenediamines,        para-aminophenols, ortho-aminophenols, heterocyclic bases        preferably comprising at least two nitrogen atoms, and addition        salts thereof; ii) optionally at least one coupler; and iii) at        least one chemical oxidizing agent; and iv) particularly at        least one basifying agent, preferably organic alkaline agent, in        particular alkanolamines such as monoethanolamine (MEA) is        applied.

Said ready-to-use composition (A) according to the invention is preparedjust before its use by extemporaneous mixing of an oxidation dyeingcomposition (A′) comprising at least one oxidation base; and ii)optionally at least one coupler, and of a composition comprising atleast one chemical oxidizing agent (composition (C) as previouslydefined).

Finally, the invention relates to a multicompartment device comprising afirst compartment containing a cosmetic composition (B) as previouslydefined, a second compartment containing a cosmetic composition (A′) aspreviously defined, and a third compartment containing a composition (C)as previously defined. According to one particular embodiment, thedevice comprises a fourth compartment comprising a composition (D)comprising one or more fatty substances, said composition (D) to bemixed with the compositions (A′) and/or (C), the fatty substance contentbeing greater than or equal to 35% by weight relative to the totalweight of the mixture of the compositions (A) to (D).

The device is suitable for implementing the dyeing process according tothe present invention.

The evaluation of the coloration can be done visually or read on aspectrocolorimeter (such as Minolta CM3600d, illuminant D65, angle 10°,SCI values) for the L*, a*, b* colorimetric measurements. In this L*,a*, b* system, L* represents the intensity of the color, a* indicatesthe green/red color axis and b* indicates the blue/yellow color axis.The lower the value of L, the darker or more intense the color. Thehigher the value of a*, the redder the shade; the higher the value ofb*, the yellower the shade. The variation in coloring between thecolored locks of natural white hair (NW) which is untreated (control)and after treatment or coloration are defined by ΔE*, corresponding tothe colour uptake on keratin fibers, according to the followingequation:

ΔE*=√{square root over ((L*=L ₀*)²+(a*−a ₀*)²+(b*−b ₀*)²)}

In this equation, L*, a* and b* represent the values measured afterdyeing the natural hair comprising 90% of white hairs and L₀*, a₀* andb₀* represent the values measured for the untreated natural haircomprising 90% of white hairs.

The greater the value of AE, the greater the difference in color betweenthe control locks and the dyed locks and the greater colour uptake is.

On the other hand for evaluating the selectivity of the color betweenthe root and tip of the keratin fiber, measurement can be done on permedor sensibilised white hair (PW) and natural white hair, wherein thevariation in coloring between the colored locks PW and the colorednatural white hair are defined by ΔE*, corresponding to the selectivityof the colour, is calculated according to the following equation:

ΔE*=√{square root over ((L*−L ₀*)²+(a*−a ₀*)²+(b*−b ₀*)²)}

In this equation, L*, a* and b* represent the values measured afterdyeing the natural hair comprising 90% of white hairs and L₀*, a₀* andb₀* represent the values measured after dyeing the permed orsensibilised hair. The lowest ΔE*, the best homogeneity of the haircolor.

If the light fastness is investigated, AE* is also calculated for theL0*, a0*, b0* and L*, a*, b* measured of the locks before and afterexposure to the light, respectively.

Chromaticity in the CIE L*, a*, b* colorimetric system is calculatedaccording to the following equation:

C*=√{square root over (a* ² +b* ²)}

The greater the value of C*, the greater the chromaticity is.

The examples that follow serve to illustrate the invention without,however, being limiting in nature.

The examples that follow serve to illustrate the invention without,however, being limiting in nature.

EXAMPLE 1 I. Compositions Tested 1/ Dyeing Process

The dyeing process consists of 3 steps:

Step 1: Application, with a brush, of 120 g of pretreatment per head, todry hair, on volunteers having at least 70% grey hair. Leave-on time: 10min at ambient temperature.

Step 2: Rinsing. Rubbing dry with an absorbent towel.

Step 3: Application of the mixture of the dyeing compositions (A) with abrush. 120 g overall. The leave-one time is 30 min at ambienttemperature.

After this leave-on time, the locks are washed with lnoa Post shampoo,rinsed and then dried. The coloration obtained is evaluated blind byhairstylists.

2/ Preparation of the Pretreatments

Two pretreatment compositions are prepared:

(B) Ingredients Invention* Oxyethylenated lauryl alcohol (2 OE) 2%(C₈/C₁₀/C₁₂/C₁₄ 34/24/29/10) Alkyl 2% Polyglucoside (1,4) as an aqueoussolution at 53%, non protected (pH 11.5 using NaOH) Acrylic polymer inemulsion 4% Hydrophobically modified inulin 4% Triethanolamine 1%2-Octyldodecanol 50%  Manganese gluconate•2 H₂O 0.4%  Chlorhexidinedigluconate in solution 0.2%  2-Phenoxyethanol 0.7%  Deionized water(qs) qs 100% *Amount: % in g for 100 g of composition (B)

3/ Preparation of the Dyeing Compositions:

Composition (A′) Ingredients % in g Ethylenediaminetetraacetic acid 0.2%Oxyethylenated oleyl alcohol (10 OE)  1% Cetyl palmitate  2% Vitamin C:L-Ascorbic acid as a fine powder 0.12%  Oxyethylenated oleyl alcohol (20OE)  4% Mixture of C₁₈ to C₂₄ linear alcohols 4.6% (C₁₈/C₂₀/C₂₂/C₂₄:7/58/30/6) alcohol content >95% Powdered sodium metabisulfite 0.22% Liquid petroleum jelly  60% Oxyethylenated decyl alcohol (5 OE) 1.2%Glycerol  5% 1-β-Hydroxyethyloxy-2,4-diaminobenzene 3.86% dihydrochloride Carboxyvinyl polymer synthesized in an 0.1% ethylacetate/cyclohexane mixture Myristyl glycol ether of Oxyethylenated0.01%  (60 OE) cetylstearyl (C₁₆/C₁₈) alcohol Pure monoethanolamine 6.3%Deionized water qs 100%

Composition C Ingredients % in g Poly[(dimethylimino)-1,3- 0.25% propanediyl(dimethylimino)-1,6-hexanediyl dichloride] Non-stabilizedpolydimethyldiallylammonium 0.5% chloride at 40% in waterDiethylenetriaminepentaacetic acid, 0.15%  pentasodium salt as a 40%aqueous solution Hydrogen peroxide as a 50% aqueous solution  12% (200vol. aqueous hydrogen peroxide solution) Tetrasodium pyrophosphate•10H₂O 0.03%  Disodium tin hexahydroxide 0.04%  Liquid petroleum jelly  20%Cetylstearyl alcohol (30/70 C₁₆/C₁₈)  6% Vitamin E: DL-alpha-Tocopherol0.1% Oxyethylenated stearyl alcohol (20 OE)  5% Protected Oxyethylenatedrapeseed acid 1.3% amide (4 OE) Glycerol 0.5% Phosphoric acid (pH) qs pHDeionized water (qs) qs 100%

At the time of use, the following are mixed: 60 g of the composition(A′) and 60 g of the composition (C) (Inoa oxidizing agent, 20 vol). Themixture obtained, ready-to-use composition (C), has a pH of 9.8.

4/ Results Obtained

The evaluation was carried out on 3 volunteers having between 75-100%grey hair. A dark chestnut brown colour is obtained. The composition ofthe invention emerges as very efficient in terms of coverage of greyhair.

Example of grading on a volunteer:

Grading scale: coverage of grey hair 5: no coverage, 6: medium coverage,7: good coverage, 8: very good coverage Pretreatment with the Volunteerscomposition of the invention (B) 1 7.5 2 7.5 3 7

Demonstration Example 2:

Pretreatment with the emulsion at 78.5% of oil vs aqueous-alcoholic gelpretreatment.

1/ Dyeing process

It is the same process as for example 1.

The dyeing process consists of 3 steps.

Step 1: Application, with a brush, of 60 g of pretreatment per half-head(comparative on one side and invention on the other), to dry hair, onvolunteers having at least 70% grey hair. Leave-on time: 10 min atambient temperature.

Step 2: Rinsing. Rubbing dry with an absorbent towel.

Step 3: Application, with a brush, of the mixture of dyeingcompositions. 120 g overall. The leave-on time is 30 min at ambienttemperature.

After this leave-time, the locks are washed with lnoa Post shampoo,rinsed and then dried. The coloration obtained is evaluated blind byhairstylists.

2/ Preparation of the Pretreatments

Two pretreatment compositions are prepared:

Comparative composition: (B₂) Ingredients % in g Manganese gluconate•2H₂O 0.4% Denatured absolute ethyl alcohol  50% Hydroxyethylcellose MW:1,300,000 1.5% Deionized water (qs) qs 100%

Composition of the invention (B′) Ingredients % in g Oxyethylenatedlauryl alcohol (2 OE)  2% (C₈/C₁₀/C₁₂/C₁₄: 34/24/29/10) Alkyl  2%polyglucoside (1,4) in aqueous solution at 53%, non protected (pH 11.5using NaOH) SMDI/polyethylene glycol polymer 0.5% bearing decyl endgroups, as a water-glycol solution Manganese gluconate•2 H₂O 0.4% Liquidpetroleum jelly 78.5%  Deionized water (qs) qs 100%3/ Preparation of the dyeing compositions

These are the same dyeing (A′) and oxidizing (C) compositions as inExample 1.

4/ Results obtained

This comparison was carried out on 3 volunteers having between 75-100%grey hair.

Example of aradina on a volunteer:

Grading scale: Coverage of grey hair 5: no coverage, 6: medium coverage,7: good coverage, 8: very good coverage Pretreatment with Pretreatmentwith the comparative the composition of Volunteer composition (B₂) theinvention (B′) 1 6.5 7.5 2 6.5 7 3 7 7.5

The process of the invention which uses as pretreatment the composition(B′) or comprising at least one metal catalyst and an amount of fattysubstance greater than or equal to 10%, of the invention, makes itpossible to significantly improve the colouration of the hair, inparticular in terms of coverage of grey hair.

1. Process for the oxidation dyeing of keratin fibres, in particularhuman keratin fibres such as the hair, implementing: a) a step ofpretreating said fibres by application to said fibres of a cosmeticcomposition (B) comprising: i) at least one fatty substance in an amountof greater than or equal to 10% by weight relative to the total weightof the composition (B), preferably in an amount of greater than or equalto 25%, more preferentially in an amount of greater than or equal to 35%by weight; and ii) at least one metal catalyst; b) optionally a washing,rinsing, drying and/or rubbing-dry step; c) followed by a step of dyeingby application to said fibres of a cosmetic composition (A) comprising:i) at least one oxidation base; ii) optionally at least one coupler;iii) at least one chemical oxidizing agent.
 2. Process according to thepreceding claim, in which the fatty substance(s) is (are) chosen fromC₆-C₁₆ hydrocarbons or hydrocarbons comprising more than 16 carbonatoms, and in particular alkanes, oils of plant origin, fatty alcohols,fatty acid and/or fatty alcohol esters, and silicones, or mixturesthereof.
 3. Process according to either one of the preceding claims, inwhich the fatty substance(s) is (are) an oil or oils, i.e. a compound orcompounds that is or are liquid at a temperature of 25° C. and atatmospheric pressure; preferably, the fatty substance is chosen frommineral oils such as liquid petroleum jelly, C₆-C₁₆ alkanes, volatilelinear alkanes, polydecenes, liquid fatty acid and/or fatty alcoholesters, and liquid fatty alcohols, or mixtures thereof, moreparticularly the fatty substance is chosen from mineral oils such asliquid petroleum jelly and fatty alcohols such as octyldodecanol. 4.Process according to any one of the preceding claims, in which thedyeing composition (A) comprises at least one fatty substance as definedin any one of the preceding claims.
 5. Process according to any one ofthe preceding claims, in which the composition (B) has a fatty substancecontent preferably ranging from 10% to 80% by weight, and even moreparticularly ranging from 20% to 75% by weight, better still from 25% to70% by weight and quite particularly from 40% to 60% by weight relativeto the total weight of the composition (B).
 6. Process according to anyone of the preceding claims, in which the composition (A) has a fattysubstance content preferably ranging from 10% to 90% by weight, and evenmore particularly ranging from 20% to 80% by weight, better still from30% to 50% by weight relative to the total weight of the composition(A).
 7. Process according to any one of the preceding claims, in whichthe metal catalyst(s) is (are) chosen from metal salts, metal oxides andmetal complexes, and mixtures thereof, in particular the metalcomplex(es) is (are) chosen from transition metal salts and rare earthmetal salts, and also mixtures thereof; in particular be made ofmanganese, iron, cobalt, copper, zinc, platinum, nickel, titanium,silver, zirconium, chromium, molybdenum, tungsten, gold and vanadium,and among said metals, quite particularly manganese.
 8. Processaccording to any one of the preceding claims, in which the metalcatalyst(s) is (are) chosen from metal salts which are inorganic, chosenfrom halides, carbonates, sulfates and phosphates, in particularoptionally hydrated halides.
 9. Process according to any one of thepreceding claims, characterized in that the metal catalysts are chosenfrom organic acid salts of transition metals, in particular ofmanganese, and inorganic salts of rare earth metals, in particular ofcerium.
 10. Process according to any one of the preceding claims, inwhich the metal catalyst(s) is (are) chosen from metal salts whichpossess a metal in oxidation state II and two (poly)hydroxy acid-derivedligands, particularly the metal salts are complexed with two carboxylategroups such as that of formula (I):R—C(O)—O—M—O—C(O)—R′  (I) and also the solvates thereof, such as thehydrates, and the enantiomers thereof, in which formula (I): Mrepresents a metal (II) or metal²⁺ in oxidation state 2, preferablymanganese, R and R′, which may be identical or different, represent a(C₁-C₆)(poly)hydroxyalkyl group.
 11. Process according to any one of thepreceding claims, in which the metal catalyst(s) is (are) organic acidmetal salts chosen from citrates, lactates, glycolates, gluconates,acetates, propionates, fumarates, oxalates and tartrates, in particulargluconates.
 12. Process according to any one of the preceding claims,which implements a step b) of rinsing and rubbing dry, preferably with acloth or an absorbent paper.
 13. Process according to any one of thepreceding claims, in which the composition (A) comprises i) at least oneoxidation base chosen from para-phenylenediamines,bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols,heterocyclic bases preferably comprising at least two nitrogen atoms,and addition salts thereof, preferably the oxidation base(s) is (are)chosen from para-phenylene diamines.
 14. Process according to any one ofthe preceding claims, in which the composition (A) comprises i) at leastone chemical oxidizing agent chosen from hydrogen peroxide, ureaperoxide, alkali metal bromates or ferricyanides, peroxygenated salts,for instance alkali metal or alkaline-earth metal persulfates,perborates, peracids and precursors thereof and percarbonates, andperacids and precursors thereof; preferably the chemical oxidizing agentis hydrogen peroxide.
 15. Process according to any one of the precedingclaims, in which the compositions (A) and/or (B) comprise at least oneorganic or inorganic, preferably organic, basifying agent in particularchosen from aqueous ammonia, alkali metal carbonates or bicarbonatessuch as, in particular, sodium carbonate, potassium carbonate, sodiumbicarbonate or potassium bicarbonate, organic amines chosen fromalkanolamines, oxyethylanated and/or oxypropylenated ethylenediamines,amino acids and the compounds of formula (III) or mixtures thereof:

in which formula (III) W is a divalent C₁-C₆ alkylene radical optionallysubstituted with one or more hydroxyl groups or a C₁-C₆ alkyl radical,and/or optionally interrupted with one or more heteroatoms such as O, orNR_(u), and R_(x), R_(y), R_(z), R_(t) and R_(u), which may be identicalor different, represent a hydrogen atom or a C₁-C₆ alkyl, C₁-C₆hydroxyalkyl or C₁-C₆ amino alkyl radical; preferentially, the basifyingagent(s) is (are) chosen from alkanolamines such as monoalkanolamines,dialkanolamines or trialkanolamines comprising one to three identical ordifferent C₁-C₄ hydroxyalkyl radicals, in particular monoethanolamine.16. Process according to any one of the preceding claims, which involvesthe following: firstly, of a composition (B) comprising i) at least 35%of fatty substances as defined in any one of claims 1 to 3 and 5, thefatty substance(s) preferably being chosen from fatty substances thatare liquid at ambient temperature and at atmospheric pressure, inparticular chosen from liquid petroleum jelly, C₆-C₁₆ alkanes,polydecenes, liquid fatty acid and/or fatty alcohol esters, liquid fattyalcohols or mixtures thereof and ii) at least one metal catalyst asdefined in any one of claims 7 to 11; and optionally iii) at least onebasifying agent as defined in claim 1 or 15, in particular chosen fromalkanolamines such as triethanolamine; then, secondly, intermediaterinsing, and rubbing dry preferably with a cloth or an absorbent paper;then, thirdly, a ready-to-use cosmetic composition (A) comprising i) atleast one oxidation base as defined in claim 1 or 13; ii) optionally atleast one coupler; and iii) at least one chemical oxidizing agent asdefined in claim 1 or 14; and iv) at least one basifying agent asdefined in claim 15, preferably organic basifying agent, in particularalkanolamines such as monoethanolamine.
 17. Multicompartment devicecomprising a first compartment containing a composition (B) as definedin any one of claims 1 to 3, 5, 7 to 11 and 15, a second compartmentcontaining a composition (A) as defined in any one of claims 1 to 4, 6,13 and 15, and a third compartment containing a composition (C)comprising one or more chemical oxidizing agents as defined in claim 1or 14.